Interaction of Dyes Used for Foods with Food Packaging

Polyester Fibers

1. ARVANITOYANNIS,’,* E. TSATSARONI,Z E. PSOMIADOU,3 and J. M. V. BLANSHARD’

’Department of Applied Biochemistry and Food Science, University of Nottingham, Sutton Bonington Campus,
Loughborough, Sutton Bonington, Leics. LEI 2 SRD, United Kingdom; 2Department of Chemistry, Laboratory of
Organic Chemical Technology, Aristotle University of Thessaloniki, 54006 Thessaloniki, Greece; 3Department of
Chemical Engineering, Loughborough University of Technology, Loughborough, Leics. LE11 3TU, United Kingdom

SYNOPSIS

The effect of pH, temperature, dye concentration, and additives on the absorption of the
dyes FD & C (Food, Drugs and Cosmetics) Blue 1 and Blue 2 upon poly(ethy1ene tere-
phthalate) (PET) and poly (butylene terephthalate) (PBT) subjected to different draw
ratios (and, thus, resulting in different percentage crystallinities determined with DSC and
wide-angle X-ray diffraction patterns) was investigated and a correlation between these
parameters and the dye uptake was suggested. The absorption kinetics of the dyes on the
polyesters were studied and a mechanism based upon the development of hydrogen bonds
between the dyes and the end groups ( - COOH, -OH) of the polyesters and the swelling
of the network was proposed. Finally, an indirect measurement of the T8 values of the
polyesters was suggested based upon the different dyeing diffusion rates. 0 1994 John Wiley
& Sons, Inc.

INTRODUCT10N ( d ) good recovery from bending and stretching;

The promotion and the consumption of a food prod-
uct is closely linked to its appetizing appearance,
which is usually, in turn, connected to its food-
packaging material. Polymeric materials usually de-
fined as “plastics” are extensively used in food-
packaging applications. To date, poly (ethylene
terephthalate) ( P E T ) , with its improved clarity, is
expected to take a growing portion of the glass re-
placement in the future.’
The following properties of polyesters2 give them
a dominant role in the packaging industry:
( a ) hydrophobic nature ( < 1?6 w / w ) ;
( b ) excellent resistance to organic solvents, light
and weathering conditions;
( c ) indifference to microorganisms;
* To whom correspondenceshould be addressed at Osaka Na-
tional Research Institute, AIST, Functional Polymer Section, 1-
8-31 Midorigaoka, Ikeda, 563 Osaka, Japan.
Journal of Applied Polymer Science, Vol. 51, 1753-1764 (1994)
0 1994 John Wiley & Sons, Inc. CCC 0021-8995/94/101753-12
( e ) low creep and considerable retention of
properties at elevated temperatures;
( f ) low gas permeability; and
( g ) transparency.
Depending on the country of PET production,
P E T is known under a variety of different names,
such as Mylar (USA), Melinex ( U K ) , Luminar
(Japan ) , and Terphane (France) .394 Similarly to
PET films, PET fibers are also known under various
trade names, the most well known of which are Ter-
ylene ( U K ) and Dacron (USA).
Both natural and synthetic dyes are used for
dyeing the polymers either superficially or through-
out their entire mass. Although, nowadays, there
exists a strong trend toward the utilization of natural
dyes, advocating their biodegradability and the con-
sumers’ health, synthetic dyes continue to prevail
over the natural dyes because of their lower price.
The synthetic dyes (for foods, drugs, and cosmetics
applications) could be concisely described as acid
dyes of low molecular weight that contain one or
more sulfonic groups in their molecule^.^-^ The
1753
1754 ARVANITOYANNIS E T AL.
eventually undesirable effects of dye migration from
foods to polyamide-packing materials has been ob-
served and several publications have dealt with it.
This migration was attributed to interactions be-
tween the amine/amide groups and the sulfonic
gro~ps.~,~,’
The dyeing properties of polyester fibers are
strongly influenced by many of the processing con-
ditions to which the fiber may be subjected during
manufacture. Of the various means for the conver-
sion of polymers to fibers, only one (melt-spinning)
is of present-day importance for polyester fiber
manufacture.
The undrawn or partially oriented yarns produced
by melt spinning and cooling the polymer are easy
to dye. Drawn materials, on the other hand, are dyed
much more slowly. During the process of drawing,
stresses are developed in the structure that tend to
align some of the molecular chain segments [pre-
viously being in the amorphous state, Fig. 1 ( a )] in
the direction of stress and cause stress-induced ori-
entation [Fig. 1( b ) 1. The resulting structure is
termed uniplanar axial orientation,’ i.e., the chain
axes of the crystals are oriented toward the machine
direction, whereas the plane of the amorphous rings
tends to be oriented parallel with the fiber surface;
ca. 10-20% of the structure is in the crystalline phase
[Fig. l ( c ) ] .
Thus, determination of the relationship between
draw ratio and the dyeing parameters for disperse
dyes on polyester fibers indicates that both the
equilibrium absorption A , and the diffusion coef-
ficient decrease with increasing draw ratio. This is
due to the increased crystallization of the fiber ma-
trix together with a slightly increased orientation,
which results in a decrease in the accessibility to
penetrating moiecules.l0*”
Consequently, the increase in the percentage
crystallinity ( % K ) of the polyesters, measured with
(a) (b) (C)
Figure 1 Fringed micelle model of PET and PBT17:
( a ) radomly oriented chains in the amorphous quenched
state; (b) radomly oriented semicrystalline structure; ( c )
uniaxially oriented semicrystalline structure.
DSC and wide-angle X-ray diffraction patterns, de-
pends greatly on the draw ratio and on the temper-
ature and time of the hot-drawing stage. Analo-
gously, high draw ratios, high temperatures ( Tg
< T < T,) ,and prolonged annealing times improved
substantially the perfection of the crystals of poly-
amides and also induced an increase in their Tgls.7312-15
In addition to our previous work on dye absorp-
tion on polyamide food packaging material^,^ we
have undertaken this study in order to examine the
mechanism and the conditions under which a dye
migration from food to polyester packaging can oc-
cur. This attempt was made in order to correlate
the draw ratios and the % crystallinity and some
structural features, e.g., Tg,and the amount of end
groups -COOH, -OH of polyesters with the dye
absorption. The effect of pH value, temperature, dye
concentration, and presence of additives on dye ab-
sorption was also studied. An indirect measurement
of Tgvalues, based upon the differences in the dif-
fusion dyeing rates, was suggested and compared to
the results obtained with differential scanning cal-
orimetry (DSC) and dynamic mechanical thermal
analyzer (DMTA). The results of polyester dyeing
(due to migration from foods) were compared to
those of polyamides and similarities / differences in
the two cases were pinpointed.
MATERIALS
Polyesters-Substrates
Polyester fibers were prepared by melt extrusion at
spinning speed 3000 rpm. Polyesters as spun fibers
were subsequently hot drawn (at T = Tg 20”C, +
i.e., at 86°C for PET and 42°C for PBT) at various
draw ratios X = 0-3.
The substrates consisted of standard 5 g samples
of the polyester fibers that were exposed to solutions
of the dyes. The polyesters were purchased from
Ciba-Geigy. The draw ratio was attained using an
apparatus elsewhere describedl6placed in a chamber
of controlled temperature. The amorphous polyes-
ters were heated to about 20°C above Tg ( a t 86 and
42°C for PET and PBT, respectively) where the
polymer molecules acquire sufficient thermal energy
and molecular mobility, allowing the fiber to be
drawn by a factor 3-4 in the machine dire~tion.’~
Dyes
Dyes were purchased from a commercial company
in the powder form as their sodium salts (Warner
Jenkinson, St. Louis, MO). Stock solutions were

prepared in distilled water at concentration of 1000
ppm. The following two dyes were used
( a ) C.I. Food Blue 1 7301518:
0 0
[2sulfonic groups] (I)
( b ) C.I. Food Blue 2 420901':
[3sulfonic groups] (11)
Apparatus
Differential scanning calorimetry (DSC ) and dy-
namic mechanical thermal analysis (DMTA) mea-
surements were carried out with a Perkin-Elmer
DSC-2 ( 10°C/min = heating rate) and PL-DMTA
(Mark 11) (2.5"C/min and 1Hz were heating rates
and frequency, respectively) described in detail in
A Philips 1020PW dif-
previous publi~ations.'~-'~
fractometer was used to record the wide-angle dif-
fraction patterns and the traces were analyzed as
previously
pH Variation
The pH of the solutions (40 ppm) was subjected to
1unit increments within a range from 1to 8, slightly
lower than the pH of most foodstuffs.2 The pH ad-
justments were made using 2.OM benzoic acid or
sodium hydroxide solutions. Substrates were ex-
posed to the dye solutions for a period of 72 h under
controlled temperature (65 and 100°C for P E T and
PBT, respectively).
Concentration Variation
The range of concentrations used was 10-60 ppm.
Six concentrations ( 10, 20, 30, 40, 50, and 60 ppm)
of dye solution were used in total as the most com-
monly used in beverage drink^.^ The solutions were
adjusted to pH 2 with 2.OM benzoic acid. Exposure
time and temperature of these substrates to the
above-mentioned six solutions were 72 h and 65 and
100°C for PET and PBT, respectively.
INTERACTION OF DYES USED FOR FOODS 1755
Temperature Effect
It was studied at the following temperatures:
PBT -20, -10, 0, 5, 10, 20, 25, 30, 40, 50, 60,
70,80,90, and 100°C
PET 0, 20, 30, 40, 50, 60, 70, 75, 80, 84, 88, 90,
92,94,96,98, and 100°C
The concentration of the dye solutions was 40 ppm
and the exposure time for all of them was 72 h.
Determination of the Dye Migration Rate
Solutions of dye (Brilliant Blue, No. 1) of 20 ppm
concentration were adjusted to pH 2 using a 2.OM
benzoic acid solution. Substrates of PET and PBT
were exposed to the dye solutions a t 10, 20, 30, 40,
50, 60, 70, and 80°C (for PBT) and at 20, 40, 50,
60,70,80,90, and 100°C (for PET) a t various time
intervals for the time range 24,48, 72, 96, 130, and
154 h. The action of the dye absorption was stopped
by immersing the substrates into liquid nitrogen re-
cipients.
Determination of the Dye Migration Mechanism
Seven solutions of 20 ppm Blue No. 1were prepared
from the stock solution. The pH of each solution
was adjusted to 2.0 with one of the following acids":
( a ) CH3COOH pKn = 4.74
COOH pKn=4.2
OH
I
( c ) HOOC-C-CH2COOH pKn = 3.13
I
COOH
(d) ClCHzCOOH pKn = 2.86
(e) ClzCHCOOH pK, = 1.26
(f ) C1,CCOOH pKn = 0.64
(g) H2S04 first pK, = -5.2
Exposure time and temperature of the polyester
( P E T and P B T ) substrates were 72 h and lOO"C,
respectively.
Effect of Additives on Dye Migration Rate
Solutions of 20 ppm dye were prepared from stock
solutions and the pH of each solution was adjusted
to pH 2.0 with 2.OM benzoic acid. Sodium chloride
1756 ARVANITOYANNIS ET AL.

( NaCl) , sodium sulfate ( Na2So,), and several sugars

such as glucose, fructose, and sorbitol were added
to produce solutions within the concentration range
0.1-1.OM.

RESULTS AND DISCUSSION

pH Effect
The pH of dye ( I ) and (11) solutions was varied
within relatively wide range (1-8). Although it was
previously reported that the pH has a pronounced
effect upon the migration of the dye to packaging
p~lyamides,~,~’ in the case of polyesters, the pH effect
is not so intense in absolute values (compared to
polyamides) , although it seems to be in relative val- 0 1 2 3 4 5 6 7
ues (Figs. 2-3 ) . The low dye migration to polyester PH -
packaging was attributed to their rigid structures Figure 3 Effect of the pH on the absorption of Blue 2
and their lack of reactive dyesites, whereas the high on PET and PBT, previously subjected to various draw
number of -NH2 end groups was held responsible ratios, at 100°C after 7 2 h (exposure time).
for the hydrogen bonding between the dyes and the
polyamide sites.7 Hydrophobic fibres, such as poly-
ester, cannot be dyed with dyes of high aqueous sol- in contact with aqueous solutions.” However, a low
ubility, as the case with acid dyes is, because the level of dye absorption is observed for both PET
ionization (and thus strongly polar behavior) in wa- and PBT, especially at high pH’s (Figs. 2 and 3 ) .
ter of the dyes produces adverse interactions with This could be attributed to the following reasons:
the fiber. Apart from size hindrance, which is en-
countered with most ionic dyes and makes penetra- i. Development of hydrogen bonding between the
carboxyl and hydroxyl end groups of the poly-

.”T
tion of these dyes difficult, electrical repulsion of
anionic dyes takes place due to the high negative ester fiber and the imino-, alkylimino-, and
surface potentials exhibited by hydrophobic fibers carboxy-groups of the dye molecules. Table I
gives the average carboxylZ1and hydroxy122end
groups of the polyesters involved in this study.
ii. The benzoic acid present in the dye solution
may have a “carrier” action by increasing
swelling of the fiber and loosening of the fiber
structureg at low pH values (Table 11).
A PET The absorption of the dye upon the polyester fiber
PET
0 PBT is favored at low pH values, especially when these
A PET 4
o m are attained with high benzoic acid contents. Figure
Q PBT 4 4 shows that, if the same pH is attained by both
strong and weak acids, it is the latter which promote
a greater dye absorption upon the polyester fibers.
Possible action of chlorinated hydrocarbon sol-
vents used recently in the dyeing of “difficult” ma-
terials (such as polyesters) 23 has also been studied
by adding dichlorobenzene to the dye solution. The
nn use of an organic solvent in the dyeing process for
0 1 2 3 4 5 6 7 8 polyester fibers may be considered to be a variant
PH - of the carrier dyeing process. Figure 5 shows that
Figure 2 Effect of the pH on the absorption of Blue 1 the higher the dichlorobenzene content, the higher
on PET and PBT previously subjected to various draw the percentage of the absorbed dye upon the poly-
ratios at 100°C after 7 2 h (exposure time). ester fiber.
 INTERACTION OF DYES USED FOR FOODS 1757

Table I Carboxy121and Hydroxy122End Groups and Percentage Crystallinity (%K)Determined with

DSC and Wide-angle X-ray Diffraction Patterns of the Polyester Samples (x f SD: Average and
Standard Deviation Determined from Five Measurements)

% Crystallinity
Carboxyl End Groups Hydroxyl End Groups
Draw Ratio Equiv -COOH/M, Equiv -OH/A& DSC X-rays

PET 0 0.45 0.62 0 0

1 0.43 0.58 3 f 0.3 4 k 0.5
2 0.46 0.61 8 t 1.0 11 f 1.3
3 0.44 0.60 14 k 1.2 15 f 1.3
4 0.45 0.61 19 f 1.5 23 f 1.4
PBT 0 0.34 0.49 0 0
1 0.38 0.50 5 k 0.4 8 f 0.9
2 0.36 0.52 12 f 1.0 15 f 1.2
3 0.35 0.49 20 f 1.5 22 f 1.4
4 0.36 0.50 26 t 2.1 31 t 2.2

Correlation Between the Dye Uptake and the
Polyester Structure
The observed significant differences a t the level of
the dye uptake between the PET and the PBT could
be attributed to their structural features and, in
particular, to flexibility / stiffness of the polymeric
chain that can facilitate the access to the dye mol-
ecules. PBT has four methylene groups (compared
to two of the P E T ) and it is therefore more flexible
than PET. The Tgof amorphous PBT is = 22"C,
whereas the Tgof amorphous PET was found to be
approximately 65-69°C.4,24,25The level of the ab-
sorbed dye upon the PBT fiber was found to be,
generally speaking, higher than PET a t various
temperatures due to the higher accessibility (greater
flexibility) higher number of -COOH and -OH
end groups7and easier penetration of the PBT net-
work (Figs. 6 and 7 ) . However, in both cases ( P E T
and PBT) , the equilibrium was achieved after con-
siderably longer time than that for polyamides, i.e.,
many hours/days compared to several minutes /
hours, thus making clear the greater difficulty that

0.0
0 1 2 3 4 5 6 7 8
PK, - 10 20 30 40 50 60 70 80 90 100
Figure 4 Effect of pK, (weak/strong acids on the ab-
sorption of dyes (Blue 1and Blue 2 ) on PET (draw ratio
-
temperature ("C)

= 0 ) and PBT at pH 1, a t 100°C after 72 h (exposure Figure 5 Effect of dichlorobenzene content on the dye
time). (Blue 2 ) absorption on PBT vs. temperature at pH 1.
 ARVANITOYANNIS ET AL.

Eil I

A 0

0.0
0 12 24 36 48 60 72
time (hours) - 84
Figure 6 Effect of temperature on the absorption of
Blue 2 on PBT (draw ratio = 0) vs. time.
the dye encounters on its migration to the polyester
substrate (Figs. 6 and 7).
The percentage crystallinity of the substrate was
also studied because it was shown in previous pub-
lications that the diffusion of the dye increases in
the amorphous regions, whereas it is rather difficult
to penetrate in the highly crystalline materi-
a1s.7,10,26,27 In an effort to induce considerable differ-
ences in the percentage crystallinity that would en-
able us to speculate about its effects on the level of
absorbed dye, the polyester samples were subjected
to various drawing ratios at temperatures higher
than their Tgfor 72 h. Table I gives the values of
the developed percentage crystallinity ( % K ) with
the draw ratio, temperature, and time. Several pre-
vious articles have described the orientation distri-
0100 A 70 0 30
sc A 95 65
090050
0 20
96 108 120 132
0.0
0 12 24 36 48 60 72 84 96 108120132
time (hours) -
Figure 8 Effect of draw ratio (from 0 to 4 ) on the ab-
sorption of Blue 2 on PBT ( a t pH 1and 100°C)vs. time-
isothermal absorption studies.
bution of free crystallites in However,
paracrystallite formation in uniaxially oriented PET
has also been reported including rotation with in-
creasing ratio.35The influence of the draw ratio on
the dye absorption of the polyester substrate is ev-
ident from the Figures 8 and 9, which show that the
higher the draw ratios and/or the longer the an-
nealing time the lower the amount of the absorbed
dye for PET. A comparison between PBT and PET
shows that drawing is more effective in the case of
PBT, because of its higher -CHZ - content, thus
---

080840
I

0.0
0 12 24 36 48 60 72 84 96 108120132

time (hours) - time (hours) -

Figure 9 Effect of draw ratio (from 0 to 4 ) on the ab-
Figure 7 Effect of temperature on the absorption of sorption of Blue 2 on PET ( a t pH 1 and 100OC)vs. time-
Blue 2 on PET (draw ratio = 0 ) vs. time. isothermal absorption studies.
 INTERACTION OF DYES USED FOR FOODS 1759

resulting in shorter times in higher percentage crys-
tallinities ( % K ) (Table I ) . Allomorphs that undergo
a unique reversible transformation a t low levels of
applied stress have been reported for PBT.35 One
phase ( a )is always present in an unstressed oriented
state and transforms to a different phase ( p ) when
the material is stressed, reverting back to the original
a-phase when the stress is released.36This behavior
is attributed to a conformational change of the tet-
ramethylene chain from a relaxed guuche-truns-
gauche to a stretched all-trans form and involves a
small change in enthalpy and volume. Both phases
have been characterized as having a triclinic unit-
cell ~ t r u c t u r e . The
~ ~ -crystal
~~ structure of P E T has
also a triclinic unit cell that has been determined
by wide-angle X-ray d i f f r a ~ t i o n(Figs.
~ ~ 10 and 11).
The crystallization kinetics of PBT involve higher
rates than that of PET; they do not require nucleat-
ing agents3' as in PET (talc, graphite, MgO, calcium
benzoate, etc.") ,but they have been only partially
in~estigated.~'.~~ PET crystallizes slowly and there-
fore is best used for applications where crystallinity
and strength can be enhanced through mechanical
orientation. On heating amorphous PET above Tg
(= 7 0 ° C ) , larger crystals and spherulites are
formed, resulting usually in brittle sample^.^ There-
fore, the significantly higher dye absorption of PBT
(to P E T ) , shown in Figures 12 and 13, could be
attributed to its higher crystallization rates, initiated
by drawing, resulting in the obstruction of the dye
molecules, whereas the same phenomenon is of less
importance for the PET because of its lower crys-
tallization rates.
Determination of Tg
The Tg's may be defined from dyeing experiments
as midpoints of the transitions from the nearly un-
dyed state, in which diffusion of the dye molecule

Figure 10 Configuration of PET molecule33:( a ) Arrangement of molecules in crystal:

above, projection normal to 010 plane; ( b ) below projection along c axis ( c ). Larger dots,
carbon; smaller dots, hydrogen; open circles, oxygen.
1760 ARVANITOYANNIS ET AL.

.
r\/
P

3
0

Figure 11 Arrangements of molecules in crystal of the a and /Iform of poly (butylene

terephthalate) 36: above, projections normal to the 010 plane for a and p forms [ ( a ) and
( c ), respectively] ; below, projection of a and p crystals along the c axis [ ( b ) and ( d ) ,
respectively].

through the substrate is extremely slow, to the nearly
equilibrium dyed state a t which the dye diffusion
rates are substantially higher.42However, it should
be mentioned that the actual Tgvalues determined
in this way are dependent both on the nature of the
dye molecule and on the structural properties of the
polyesters. Table I11 summarizes the Tgvalues ob-
tained with this method, with DSC and with DMTA
measurements. Table I11 shows that the Tgvalues
obtained from the DSC (midpoint of the change in
heat capacity), DMTA (defined as the loss modulus
peak), and the dyeing diffusion rates (midpoint of
transition) are in satisfactory agreement (differ-
ences 2-4") , i.e., deviation 10-15%, which lies within
the margin of experimental errors predicted for every
method. The observed increase in Tgwith the in-
crease in percentage crystallinity ( % K ) , at various
draw ratios, is attributed to the restrictive influence
of the developed crystallites on the surrounding
noncrystalline (amorphous) material (Table 111)
and is in agreement with the results of previous in-
vestigations on the polyamides, 42 isotactic polysty-
rene, poly (ethylene oxide), and poly-e-caprolac-
tone.43However, exactly the opposite trend was ob-
served (higher draw ratios induced lower T,'s) for
a number of polymers such as isotactic polypropyl-
ene and poly-4-methyl-1-pentene among others,44-46
which makes apparent the need for further inves-
tigation on the effect of annealing and/or draw ratio
upon the Tgof polymers.
 INTERACTION OF DYES USED FOR FOODS 1761

1 ratio
Table I1 Acids Used for the pH Adjustment
and their p K a

Acid PKa
=I-
t
{: 5.0 CH,COOH 4.74
In-
n m
m e
-In COOH 4.2
NT1
w = I
&
F
W I
%>

zg a2
2.5
f OH
c
0
I
HOOCHzC-C-CH2COOH 3.13
I
0.0 COOH
-10 0 10 20 30 40 50 60 70 80 100
temperature (TI - 91)
ClCH,COOH 2.86

Figure 12 Effect of draw ratio (from 0 to 4 ) on the ClzCHCOOH 1.26

absorption of Blue 2 on PET vs. temperature (at pH 1 ) . C1,COOH 0.64
H2SO4 -5.2
Dye Concentration Effects
The influence of the concentration of the dye so-
for the dye absorption results in the above low dye
lutions (Blue l and Blue 2 ) on the dye absorption
uptake values on both PET and PBT.
upon the substrates ( P E T and PBT) was studied
and the results are shown in Figure 14. Figure 14
shows that even at very low dye concentrations ( Temperature Effect
mol/L) the dye uptake for both dyes on the polyester
The influence of temperature on the dye absorption
fiber is very low (I 7.5% in most cases). The dye
of the polyesters was studied for Blue 1 and amor-
uptake is favored by higher amounts of -COOH
phous and semicrystalline PBT and PET (Table
and -OH end groups as it had happened in pre-
IV) . Figures 6 and 7 show that the dye absorption
vious investigation of polyamides where the end
increases with an increase in temperature, which is
groups were -NH2 and -COOH group^.^ How-
in agreement with the results of similar studies on
ever, the limited importance of hydrogen bonding
p o l y a r n i d e ~ . At
~ * very
~ , ~ ~low temperatures, i.e., -20,

-
temperature VC) - mol Dye/l

Figure 14 Effect of dye concentration (mol/L) on the

Figure 13 Effect of draw ratio (from 0 to 4 ) on the absorption of dyes (Blue 1 and Blue 2 ) on PET and PBT
absorption of Blue 2 on PBT vs. temperature at pH 1. at pH 1, at 100°C and after 72 h (exposure time).
1762 ARVANITOYANNIS ET AL.

Table I11 Glass Transition (T,)Values Determined with DSC, DMTA, and Dyeing Diffusion Rates

Glass Transitions ("C)

DMTA
Dyeing Diffusion
Draw Ratio DSC E" a E' tan 6" Rates

PET 0 57.5 f 2.1 60.2 f 3.2 56.4 f 1.8 63.2 f 2.3 60.5
1 63.0 f 2.5 62.7 t 2.1 60.1 f 2.3 66.8 f 2.4 64.0
2 64.3 f 1.8 65.1 f 2.4 61.9 t 2.4 70.3 f 3.0 66.0
3 68.1 f 2.3 70.3 * 2.5 64.5 t 2.6 74.8 t 1.4 69.0
4 70.2 f 3.1 72.4 f 1.9 67.9 f 2.5 78.9 f 2.1 71.0
PBT 0 18.6 f 1.3 20.4 f 1.8 17.1 f 2.1 22.8 f 1.7 19.0
1 21.4 f 2.0 24.7 f 2.1 19.0 k 1.4 27.9 f 2.0 23.0
2 30.2 f 1.7 28.2 f 1.5 24.6 f 1.6 33.5 f 3.2 30.0
3 38.7 f 1.6 39.3 f 1.4 32.7 t 2.0 42.4 f 2.3 40.0
4 47.9 f 1.8 48.7 f 2.0 41.2 f 1.8 52.3 f 1.8 50.0

* E' = storage modulus.

E" = loss modulus.
6: tan 6 = E"/E'.

-10, and O"C, there was no measurable dye absorp-
tion on the polymer substrate. The effect of tem-
perature on the dye absorption was also studied at
different draw ratios for PET and PBT (Figs. 12
and 1 3 ) . Figure 12 shows that at temperatures
< 3OoC, Blue 2 uptake on PET is insignificant for
all the draw ratios applied, whereas on PBT, even
at low temperatures (> 0°C) ,a slight dye absorption
is observed mainly for draw ratios 0-2 (Fig. 13).
Finally, the effect of temperature on the dyeing
rate of PET and PBT for the dye Blue 2 was studied
and the results are given in Table V. Table V shows
that for a given draw ratio half-dyeing time increases
with increasing temperature, since the A, values
are increasing, as has already been mentioned.
dyeing rates.7*27,47-49
However, their applicability to
the determination of dyeing rates both for
polyamides7 and polyesters with Blue 1 and Blue 2
was found to be very limited. Therefore, the deter-
mination of half-dyeing time has been suggested as
a convenient method for providing numerical values.
Half-dyeing time ( t l I z )is the time required for the
fiber to absorb half as much dye as it will absorb in
the equilibrium state. The dyeing rate is described
in terms of sigmoid time absorption isotherms. The
method for describing t I l 2and the percentage of ab-
sorbed dye ( A ) was to measure first the equilibrium
exhaustion (Figs. 8 and 9 ) and then to determine
from the curve the time at which the A / 2 absorption

Table V Half-dyeing Times (tip, h) for PET and

Determination of Dye Absorption Rate PBT by Blue 2 at Different Temperatures at
Several hyperbolic and exponential equations have Draw Ratio = 0
been suggested in the past for determining the
PBT PET

Table IV Half-dyeing Times ( t l l z )for PET and ("(2) t112 ("(2) tllP
PBT by Blue 1 at 100°C
-10 5 20 15.0
PET PBT 0 9 30 17.0
10 37.5 40 18.0
Draw Ratio ti/z (h) Draw Ratio tip (h) 19 33.0 60 20.0
22 24.0 65 22.0
0 11 0 14 30 21.0 70 21.0
1 14.5 1 18.5 60 22.5 80 21.0
2 21 2 20 80 19 90 22.0
3 18 3 18.5 100 13.5 95 16.5
4 22 4 23 100 10.5
 INTERACTION OF DYES USED FOR FOODS 1763

( a ) amorphous polyesters not previously mon-

Additive Y2.E oaxially or biaxially drawn or annealed at tem-
0 Glucose/NaCI PBT

. A GlucoselNaCl PET Blue 2 peratures above their Tg;

c
P
I
10.0

1
0 GlucoseINaCI
0 Glucose/NaCI
A GlucoselNaCl
Glucose/NaCI
I 1{PBT
PET
PET
PBT
Blue 1

I
( b ) pH 1-3;
( c ) high number of -COOH and -OH end
t
n
5 7.50
L9
n
“
I
u --
nl n groups; and
( d ) storage temperatures considerably higher
than their Tg‘s ( b 22°C and 9 68°C for amor-
phous PBT and PET, respectively).

REFERENCES

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0.0
mol (salt or sugar)/l
Figure 15 Effect of additives (glucose, sodium chloride)
on the absorption of dyes (Blue 1 and Blue 2 ) on PET
and P B T at pH 1 at T = 100°C.
occurred. Tables IV and V give the half-dyeing times
( t l p ) for various draw ratios of P E T and PBT. It
is evident that the half-dyeing times are longer for
high draw ratios (both for PET and P B T ) , which
means that the dyeing rates reach equilibriums lower
than the substrates subjected to low draw ratios.
Long half-dyeing times ( t l I z )for high draw ratios
could be attributed to the perfection of crystallites
both at the levels of molecule and network.
In addition, PBT showed longer dyeing times
than did P E T both at low and high draw ratios,
which could be attributed to the higher amount of
end groups in PET and faster development of crys-
tallinity in PBT3’ (Table I ) , respectively.
Effect of Additives
The influence of the addition of a sugar (glucose,
sucrose) or a salt ( NaCl) solution on the absorption
of Blue 1and Blue 2 was investigated and is shown
in Figure 15. No alteration in the dye absorption
rate of the polyester ( P E T and PBT) was observed,
as was the case with polyamides7 and polycapro-
la~tam.~
CONCLUSIONS
Polyester fibers (PET, P B T ) , which could even-
tually come in contact with dyes, might present
staining problems only after the following condi-
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Received June 9, 1993
Accepted August 22, 1993